US8618009B2 - Conjugated polyelectrolyte capsules: light activated antimicrobials - Google Patents
Conjugated polyelectrolyte capsules: light activated antimicrobials Download PDFInfo
- Publication number
- US8618009B2 US8618009B2 US13/128,571 US200913128571A US8618009B2 US 8618009 B2 US8618009 B2 US 8618009B2 US 200913128571 A US200913128571 A US 200913128571A US 8618009 B2 US8618009 B2 US 8618009B2
- Authority
- US
- United States
- Prior art keywords
- polyelectrolyte
- hcpe
- conjugated
- microcapsules
- microbes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/701—Integrated with dissimilar structures on a common substrate
- Y10S977/712—Integrated with dissimilar structures on a common substrate formed from plural layers of nanosized material, e.g. stacked structures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/903—Specified use of nanostructure for conversion, containment, or destruction of hazardous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- Microbes with antimicrobial properties are of interest for medical facilities, medical devices, and even homes and household items to reduce the transmission of diseases and other malaise from one organism to another organism through common contact with the surface.
- Microbes generally have a limited lifetime on a surface; however that lifetime is generally for at least a few hours and is often in the order of days. Even when the microbes survive for hours significant contact can occur over that period.
- the most prevalent technologies used for antimicrobial surfaces include: silver ion technology; organic biocides in coatings or incorporated into objects; and cationic biocides covalently bonded to a reactive silicone compounds.
- Silver ion technology in its simplest form is a coating system formed by binding silver ions to a fine ceramic powder, dispersed in a carrier. The silver ions, which can interrupt critical functions of microorganisms, are then exchanged with other ions when the surface comes into contact with aqueous fluids.
- This technology has been used to treat steel ducting and components in HVAC systems, building materials, laminates, floors, walls, paints, carpets, cubicle curtains, lockers, safety cabinets, bedpans, sack holders, soap dispensers, keypads, medical devices, wound dressings and implants.
- Organic biocides have been incorporated into plastic and fabrics during manufacture. The concentration of biocide is optimized to provide adequate protection. Many different organic biocides are now in use, some specially selected for specific applications. Some of the earliest applications involved combating the growth of odor causing bacteria on medical devices. Applications for the building industry include wall laminates, for hospital environments include bedding, bed frames, carts for transport of medication, linens, hand rails, pulls, trims, door handles, slings, hoists, window blinds, dental trays, incise drapes, wound dressings, keyboards and other equipment.
- Biocides covalently bonded to a reactive silicone compound are fixed onto a surface as an extremely thin film with little effect to the physical properties of the surface. Fixation of the biocide is important where toxicity, taint and other organoleptic aspects are of concern.
- This method is a bacteriostatic surface treatment that allows and requires normal cleaning procedures to maintain the biocidal activity of the surface.
- the technology has been used for treatment of bedsheets, hospital garments, curtains, floor and wall materials, air filtration systems, medical devices, bandages, surgical instruments and implants.
- the technique has been used to prevent biofilm growth on catheters, stents, contact lenses and endotracheal tubes.
- Antimicrobial polymers have the potential to exist in many different structural forms where enhancements, such as the surface area to volume, can significantly increase their activity toward microbes relative to surface fixed antimicrobial agent. Hence, a polymer that is a high molecular weight light activated antimicrobial agent is an attractive solution to many limitations of present antimicrobial system.
- An embodiment of the invention is a hollow conjugated polyelectrolyte (HOPE) microcapsule where at least one conjugated polyelectrolyte is in association with at least one complementary polyelectrolyte in the shape of a microcapsule with a hollow core.
- the conjugated polyelectrolyte is a polymer with a multiplicity of charged repeating units with at least a portion of the charged repeating units forming a pi-conjugated sequence.
- the complementary polyelectrolyte is one where a plurality of repeating units has a charge that is opposite the charge on the repeating units of the conjugated polyelectrolyte, such that charges on the polyelectrolytes associate through ion-pairing of some of the repeating units of the two polyelectrolytes.
- the complementary polyelectrolytes can also be a conjugated polyelectrolyte.
- the HCPE microcapsules can be 0.5 to 100 ⁇ m in cross-section, for example about 4 to about 6 ⁇ m in cross-section, and can be monodispersed in size distribution.
- the HCPE microcapsule can be formed from the complementary conjugated polyelectrolytes PPE-SO 3 ⁇ and PPE-4 + .
- a plurality of polyelectrolytes can exist as a plurality of layers where adjacent layers have complementary charges on the polymer.
- Another embodiment of the invention is a method of preparing (HCPE) microcapsules where a sacrificial core is coated with a polyelectrolyte layer and additionally coated on the exterior polyelectrolyte layer with an additional polyelectrolyte layer.
- the additional polyelectrolyte has repeating units of a complementary charge to the polyelectrolyte upon which it is deposited.
- successive additional coatings of additional complementary polyelectrolytes can be deposited where the deposited polyelectrolyte has repeating units of a complementary charge to the polyelectrolyte upon which it is deposited.
- At least one of the polyelectrolytes used to form the HCPE microcapsule is a conjugated polyelectrolyte.
- the sacrificial core is a salt particle with low water solubility.
- the core can be removed by dissolving a species formed from the salt particle by contacting the salt particle with an acid, base, metal complexing agent or any combination thereof to form the HCPE microparticle.
- a monodispersed MnCO 3 particle can be prepared and a PPE-SO 3 ⁇ conjugated polyelectrolyte can be coated from aqueous solution on the MnCO 3 core, a complementary PPE-4 + conjugated polyelectrolyte can be coated from aqueous solution on the PPE-SO 3 ⁇ conjugated polyelectrolyte and EDTA can be added to decompose the MnCO 3 sacrificial core and dissolve the resulting complexed MnEDTA salt.
- HCPE microcapsules can be used in a method for killing microbes where a plurality of hollow conjugated polyelectrolyte (HCPE) microcapsules is contacted with a medium suspected of containing microbes and irradiating the (HCPE) microcapsules with visible light, ultraviolet light or other electromagnetic radiation to kill the microbes contacted by one or more of the polyelectrolyte (HCPE) microcapsules.
- the medium can be an aqueous medium.
- FIG. 1 shows scanning electron and fluorescence microscope images at different stages of preparation of HCPE microcapsules where: (a) shows a SEM image of a MnCO 3 core before coating; (b) shows a fluorescence microscope image of CPE microparticles before removal of the sacrificial cores; and (c) shows a fluorescence microscope image of a flattened HCPE microcapsule with a creased surface; (d) shows a SEM image of a flattened HCPE microcapsule with a creased surface.
- FIG. 2 shows the chemical structure of an anionic conjugated polyelectrolyte (PPE-SO 3 ⁇ ) according to an embodiment of the invention and a cationic conjugated polyelectrolyte (PPE-4 + ) according to an embodiment of the invention.
- PPE-SO 3 ⁇ anionic conjugated polyelectrolyte
- PPE-4 + cationic conjugated polyelectrolyte
- FIG. 3 shows confocal microscope images of HCPE microcapsules with (a) live trapped bacteria before irradiation and (b) dead trapped bacteria after 15 minutes of irradiation.
- FIG. 4 shows a central slice of large clusters with entrapped dead bacteria after 1 hour exposure to white light.
- FIG. 5 shows HCPE microcapsules with entrapped bacteria where the microcapsules display (a) fibrillar structures, filaments, and (b) and (c) sheet-like structures.
- Embodiments of the invention are directed to hollow conjugated polyelectrolyte (HCPE) microcapsules that have antimicrobial properties when irradiated with electromagnetic radiation.
- the HCPE microcapsules display effective antimicrobial action against bacteria, viruses, fungi or other microbes that associate with the HCPE microcapsules, which acts as an efficient trap where the trapped microbes are efficiently killed upon irradiation.
- the microbes can be entrapped within or attached to the external surface of the HCPE microcapsules. Not to be bound by a theoretical mechanism, the light-activated antimicrobial activity is consistent with the generation of singlet oxygen and possibly successor reactive oxygen intermediates at the photoexcited HCPE microcapsule upon irradiation.
- the HCPE microcapsules comprise a plurality of layers of polyelectrolytes of complementary charge where at least one polyelectrolyte is a conjugated polyelectrolyte.
- the layers are formed about a sacrificial core.
- the sacrificial cores are monodispersed in size to allow the formation of monodispersed HCPE microcapsules upon removal of the sacrificial cores.
- the conjugated polyelectrolytes can be adsorbed on the sacrificial cores in a layer-by-layer fashion were the first layer can be either a cationic polyelectrolyte or an anionic polyelectrolyte.
- one or more conjugated polyelectrolytes can be bound to a non-conjugated polyelectrolyte, where the conjugated polyelectrolyte is capable of contacting an external bacteria or other microbial agent.
- the sacrificial cores can be of any material that effectively associates with a polyelectrolyte and can be removed after construction to form the HCPE microcapsules.
- the core can be any particulate material or suspended liquid droplet that can promote the formation of a layer of an anionic or cationic polyelectrolyte on its surface, yet can be removed after formation of the desired number of polyelectrolyte layers on the surface.
- the core can be removed in any fashion that does not damage the HCPE microcapsules, for example the removal can be any method of dissolving, vaporizing, and/or degradation of the sacrificial core.
- the sacrificial core is relatively monodispersed in size.
- the monodispersed cores have non aggregated cores that have a standard deviation in size that is less than about 25% of the mean size, for example, less than 10% of the mean size.
- the sacrificial core is a salt particle that is of low solubility in water.
- Salts that can be used as the sacrificial cores include, but are not restricted to, carbonates, oxides, chalcogenides, and other salts.
- Useful salts include those that can be decomposed using an acid or base, or dissolved using a metal complexing agent, such as ethylenediaminetetraacetic acid (EDTA).
- EDTA ethylenediaminetetraacetic acid
- the salt particle can be prepared by any method where the size can be restricted to a particular desired size range, for example less than 100 ⁇ m, for example 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 or 0.1 ⁇ m.
- a microcapsule for purposes of the invention can be a nanocapsule where the size is less than 1 ⁇ m.
- the particles can be selected by size using sieves for isolation of a particular size distribution out of a source that is polydispersed in size or particles of a selected size and/or distribution can be achieved by direct formation of particles by any method where nucleation and propagation of particle formation can be controlled.
- monodispersed metal carbonate particles for example MnCO 3 particles, can be formed as taught in Zhu et al., Chem. Mater. 2005, 17, (9), 2323-8, and is incorporated herein by reference.
- the standard deviation in size can be less than 10% of a mean size that can be, for example, less than 10 ⁇ m in size.
- the conjugated polyelectrolytes can be poly(phenylene ethynylene), poly(phenylene vinylene), poly(acetylene), poly(phenylene), poly(pyrrole), poly(furan), poly(thiophene) or any other conjugated polymer or copolymer where a sufficient number of side groups include non-hydrolyzable ionic side groups where each ionic side group can contain one or more atoms having a unit charge centered.
- the side groups can contain anionic groups, such as sulfonate, phosphonate, carboxylate, oxide, sulfide, sulfinate, phosphonate, thiosulfate, or any other anionic group that can be attached via a substituted or unsubstituted linking group, such as an alkylene, phenylene, or alkylene or phenylene group including one or more heteroatoms that links the ionic group to the polymer backbone in a regular or random manner.
- anionic groups such as sulfonate, phosphonate, carboxylate, oxide, sulfide, sulfinate, phosphonate, thiosulfate, or any other anionic group that can be attached via a substituted or unsubstituted linking group, such as an alkylene, phenylene, or alkylene or phenylene group including one or more heteroatoms that links the ionic group to the polymer backbone in a regular or random manner.
- the side groups can contain cationic groups, such as ammonium, pyridinium, phosphonium, or metal ions captured by a crown ether, cryptand, or carcerand units or any other cationic group that can be attached via a substituted or unsubstituted linking group, such as an alkylene, phenylene, or an alkylene or phenylene group including one or more heteroatoms that links the ionic group to the polymer backbone in a regular or random manner.
- cationic groups such as ammonium, pyridinium, phosphonium, or metal ions captured by a crown ether, cryptand, or carcerand units or any other cationic group that can be attached via a substituted or unsubstituted linking group, such as an alkylene, phenylene, or an alkylene or phenylene group including one or more heteroatoms that links the ionic group to the polymer backbone in a regular or random manner.
- an anionic conjugated polyelectrolyte can be deposited as a layer on the sacrificial core, followed by deposition of a complementary cationic conjugated polyelectrolyte.
- the repeating units of the two complementary conjugated polyelectrolyte can be identical except for the ionic side group, for example with the same conjugated repeating unit structure, the position of the ionic side groups can be equally spaced along the conjugated backbone with an equivalent charge on every side group.
- the side groups can have unequal charge, for example a cationic side group can have a charge of +2 and the paired anionic side group of the complementary conjugated polyelectrolyte can have a charge of ⁇ 1.
- the sacrificial core can stabilize the microcapsule shape such that the HCPE microcapsule upon removal of the core can slowly undergo a metamorphosis in shape or the HCPE microcapsule can retain the shape resulting after deposition of the polyelectrolytes on the core.
- one of the complementary polyelectrolytes need not be conjugated.
- a non-conjugated anionic polyelectrolyte such as polystyrene sulfonate
- a non-conjugated cationic polyelectrolyte such as poly(N-alkyl-4-vinylpyridinium halide)
- an anionic conjugated polyelectrolyte can be paired with an anionic conjugated polyelectrolyte.
- contact is made between suspensions of the HCPE microcapsules with microbes that result in an association.
- the HCPE microcapsules can be isolated, or aggregated into clusters in these contacted suspensions.
- a typical mixture can display dimeric and other larger clusters of HCPE microcapsules.
- clusters of 2, 4 and up to 12 HCPE microcapsules can form.
- Clustered HCPE microcapsules can form stronger associations with the microbes.
- the HCPE microcapsules can form features that increase the surface area of the paired conjugated polymers.
- a HCPE microcapsule can radiate fibrils in the presence of microbes to increase the surface area of the HCPE microcapsule. Trapping of microbes can be enhanced by the formation of fibrils or sheet-like structures.
- association of the microbes with the HCPE microcapsules does not result in high killing of the microbes in the dark. However, upon irradiation with light, the microbes are very effectively killed, where the strength of the association and the rate and extent of killing is enhanced by clustering of the HCPE microcapsules and microbes. Irradiation can be for short periods of time to extended periods of time. For example, the irradiation can be for less than 1 minute to more than 4 hours. Irradiation can be carried out concurrently or subsequently to the mixing of the HCPE microcapsules and the microbes. Irradiation can be carried out with a broad spectrum of light or with a portion of the spectrum which promotes the killing.
- HCPE microcapsules Light in the visible or ultraviolet range of the spectrum may be employed.
- HCPE microcapsules can be generated from various CPEs the necessary range must be established for a specific HCPE microcapsule, which can be readily determined by normal experimentation by one skilled in the art.
- Monodispersed MnCO 3 microparticles were prepared where nanoparticles from dilutes salt solutions of MnSO 4 and NH 4 HCO 3 were used as “nanoseeds” to initiate crystal growth without significant nucleation during the crystal growth process such that relatively monodispersed MnCO 3 microparticles were formed.
- the nanoseeds were suspended in a MnSO 4 solution which was vigorously mixed with a NH 4 HCO 3 solution to give either smooth cubical MnCO 3 particles or spherical particles depending upon the rate of mixing using a stirrer.
- the MnCO 3 microparticles were 4 to 6 ⁇ m in cross section.
- Typical mean particle size was 4.5 to 5.0 ⁇ m with a standard deviation of 0.3 to 0.5 ⁇ m, as indicated by scanning electron microscopy (SEM) and dynamic light scattering (DLS) analysis.
- Spherical shaped particles can be seen in the SEM image shown in FIG. 1( a ) where the particles display a rough surface with an aggregation of small rectangular crystals forming the spherical particles.
- DLS data show monodispersed particles in the 4 to 6 ⁇ m range where 92 to 98% of the particles are isolated particles and 2 to 8% of the particles forming aggregates in the 8 to 12 ⁇ m range.
- An exemplary DLS trace shows a mean particle size of 4.568 ⁇ m with a standard deviation of 0.387 ⁇ m representing 98% of the sample with 2% aggregate.
- CPEs were formed by a Layer-by-Layer deposition technique. Suspensions of MnCO 3 particles in 0.5 M NaCl were prepared with vigorous stirring and sonication of the suspensions. A CPE, PPE-SO 3 ⁇ , shown in FIG. 2 , was introduced from solution to the suspension and the suspension stirred for 15 minutes. After centrifugation and washing of the particles, with 0.2 M NaCl the particles were resuspended in 0.5 M NaCl followed by addition of the complementary CPE, PPE-4 + , shown in FIG. 2 , solution to the suspension to form a second CPE layer. The formation of 4 bilayers on the particles was followed by fluorescence and confocal microscopy analysis.
- Fluorescence microscopy showed emissive CPE layers and uniformly coated microparticles, as can be seen in FIG. 1( b ). Confocal microscopy images revealed, in addition to the fluorescent characteristics of the particles, uncoated MnCO 3 surfaces refracted light form particles.
- Coated particles were treated with a 0.2 M EDTA solution in 1.5 to 3 mL centrifuge vials. The formation of bubbles occurred upon introduction of the EDTA solution. The particles were flushed with solution using a pipette and centrifuged after 30 minutes and treated a second time with 0.2 M EDTA. Upon complete removal of the MnCO 3 , HCPE capsules were isolated by three cycles of washing with purified water and centrifugation. Analysis of the HCPE microcapsules by fluorescence microscopy with a 100 ⁇ oil immersion objective resulted in images where small creased features appeared on the HCPE walls, as shown in FIG. 1( c ). The HCPE microcapsules assumed a flattened appearance, as shown in FIG. 1( d ). The HCPE microcapsules retained the cross section of 4-6 ⁇ m.
- Pseudomonas aeruginosa and Cobetia marina were raised in a chemostat as described in Chemburu et al., Langmuir 2008, 24, (19), 11053-62. Confocal fluorescence microscopy was used to monitor the association of the bacteria with the HCPE microparticles. Bacterial viability was determined by staining with a 1:1 mixture of SYTO 60 and SYTOX green stains from Molecular Probes. The DNA stains produced red ( ⁇ 650 nm) and green ( ⁇ 530 nm) emissions for live and dead bacteria respectively.
- FIG. 3( a ) shows that bacteria associate on the surface and within the interior of the HCPE microcapsules. A ratio of more than 7 to 1 was observed for live to dead bacteria associated with the HCPE microcapsules.
- FIG. 3( b ) shows a fused pair of HCPE microcapsules associated with Pseudomonas aeruginosa that have been irradiated with visible light. The green fluorescence indicated that most of the bacteria are dead. When Pseudomonas aeruginosa is associated with paired HCPE microcapsules visible light irradiation results in the rapid killing of most bacteria. When HCPE microcapsules are agglomerated into larger clusters the killing efficiency of the HCPE microcapsules is enhanced.
- FIG. 4 shows large clusters of 4 to 12 HCPE microcapsules, particularly abundant are clusters of 4 HCPE microcapsules in a tetrahedral orientation to each other.
- the killing of all Pseudomonas aeruginosa is apparent in FIG. 3 . In all cases oxygen was present. Otherwise equivalent filled CPE microcapsules show inferior killing of microbes upon irradiation.
- FIG. 5 illustrates that with time fibrillar structures extend from the microcapsules, as clearly shown in FIG. 5( a ). These fibrillar structures, and sheet-like structures of FIG. 5( b )-( c ), are highly effective at capturing bacteria. These structures appear to have a hydrogel consistency.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/128,571 US8618009B2 (en) | 2008-11-10 | 2009-11-09 | Conjugated polyelectrolyte capsules: light activated antimicrobials |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11286708P | 2008-11-10 | 2008-11-10 | |
PCT/US2009/063715 WO2010054304A2 (en) | 2008-11-10 | 2009-11-09 | Conjugated polyelectrolyte capsules: light-activated antimicrobials |
US13/128,571 US8618009B2 (en) | 2008-11-10 | 2009-11-09 | Conjugated polyelectrolyte capsules: light activated antimicrobials |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/063715 A-371-Of-International WO2010054304A2 (en) | 2008-11-10 | 2009-11-09 | Conjugated polyelectrolyte capsules: light-activated antimicrobials |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/092,409 Division US9005540B2 (en) | 2008-11-10 | 2013-11-27 | Conjugated polyelectrolyte capsules: light activated antimicrobials |
Publications (2)
Publication Number | Publication Date |
---|---|
US20110293470A1 US20110293470A1 (en) | 2011-12-01 |
US8618009B2 true US8618009B2 (en) | 2013-12-31 |
Family
ID=42153615
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/128,571 Active 2029-11-18 US8618009B2 (en) | 2008-11-10 | 2009-11-09 | Conjugated polyelectrolyte capsules: light activated antimicrobials |
US14/092,409 Active US9005540B2 (en) | 2008-11-10 | 2013-11-27 | Conjugated polyelectrolyte capsules: light activated antimicrobials |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/092,409 Active US9005540B2 (en) | 2008-11-10 | 2013-11-27 | Conjugated polyelectrolyte capsules: light activated antimicrobials |
Country Status (2)
Country | Link |
---|---|
US (2) | US8618009B2 (en) |
WO (1) | WO2010054304A2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9005540B2 (en) | 2008-11-10 | 2015-04-14 | University Of Florida Research Foundation, Inc. | Conjugated polyelectrolyte capsules: light activated antimicrobials |
WO2016115362A1 (en) * | 2015-01-14 | 2016-07-21 | Whitten David G | Conjugated polyelectrolytes and methods of using the same |
US9527806B2 (en) | 2010-07-13 | 2016-12-27 | Stc.Unm | Structure, synthesis, and applications for poly (phenylene) ethynylenes (PPEs) |
US9549549B2 (en) | 2011-08-03 | 2017-01-24 | Stc.Unm | Antimicrobial materials and methods |
US9968698B2 (en) | 2013-11-08 | 2018-05-15 | Stc. Unm | Charged singlet-oxygen sensitizers and oppositely-charged surfactants |
US10533991B2 (en) | 2014-03-14 | 2020-01-14 | Stc.Unm | P-phenylene ethynylene compounds as bioactive and detection agents |
US10772851B2 (en) * | 2017-02-03 | 2020-09-15 | Aaron Kurt Neumann | Treatment and prevention of fungal infections |
US11154059B2 (en) | 2017-09-22 | 2021-10-26 | David G. Whitten | Substituted thiophene oligomers and polymers |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6151189B2 (en) * | 2010-12-30 | 2017-06-21 | ヤヴァ テクノロジーズ インコーポレイテッドYava Technologies Inc. | Transition metal compound particles and production method |
US11101396B2 (en) | 2015-11-30 | 2021-08-24 | The Regents Of The University Of California | Complementary conjugated polyelectrolyte complexes as electronic energy relays |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4251386A (en) * | 1977-07-27 | 1981-02-17 | Fuji Photo Film Co., Ltd. | Method for preparing microcapsules |
US20050148254A1 (en) * | 2003-12-30 | 2005-07-07 | Liangde Lu | Light-activated biocidal polyelectrolytes |
US20070215841A1 (en) * | 2004-05-14 | 2007-09-20 | Sonydeutschland Gmbh | Composite Materials Comprising Carbon Nanotubes and Metal Carbonates |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8618009B2 (en) | 2008-11-10 | 2013-12-31 | Stc.Unm | Conjugated polyelectrolyte capsules: light activated antimicrobials |
-
2009
- 2009-11-09 US US13/128,571 patent/US8618009B2/en active Active
- 2009-11-09 WO PCT/US2009/063715 patent/WO2010054304A2/en active Application Filing
-
2013
- 2013-11-27 US US14/092,409 patent/US9005540B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4251386A (en) * | 1977-07-27 | 1981-02-17 | Fuji Photo Film Co., Ltd. | Method for preparing microcapsules |
US20050148254A1 (en) * | 2003-12-30 | 2005-07-07 | Liangde Lu | Light-activated biocidal polyelectrolytes |
US20070215841A1 (en) * | 2004-05-14 | 2007-09-20 | Sonydeutschland Gmbh | Composite Materials Comprising Carbon Nanotubes and Metal Carbonates |
Non-Patent Citations (9)
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9005540B2 (en) | 2008-11-10 | 2015-04-14 | University Of Florida Research Foundation, Inc. | Conjugated polyelectrolyte capsules: light activated antimicrobials |
US10750746B2 (en) | 2010-07-13 | 2020-08-25 | University Of Florida Research Foundation, Inc. | Structure, synthesis, and applications for poly (phenylene) ethynylenes (PPEs) |
US10092000B2 (en) | 2010-07-13 | 2018-10-09 | Stc.Unm | Structure, synthesis, and applications for oligo phenylene ethynylenes (OPEs) |
US9527806B2 (en) | 2010-07-13 | 2016-12-27 | Stc.Unm | Structure, synthesis, and applications for poly (phenylene) ethynylenes (PPEs) |
US10174042B2 (en) | 2010-07-13 | 2019-01-08 | Stc.Unm | Structure, synthesis, and applications for poly (phenylene) ethynylenes (PPEs) |
US10058099B2 (en) | 2011-08-03 | 2018-08-28 | Stc.Unm | Antimicrobial materials and methods |
US9549549B2 (en) | 2011-08-03 | 2017-01-24 | Stc.Unm | Antimicrobial materials and methods |
US9968698B2 (en) | 2013-11-08 | 2018-05-15 | Stc. Unm | Charged singlet-oxygen sensitizers and oppositely-charged surfactants |
US10533991B2 (en) | 2014-03-14 | 2020-01-14 | Stc.Unm | P-phenylene ethynylene compounds as bioactive and detection agents |
JP2018506578A (en) * | 2015-01-14 | 2018-03-08 | ジー. ウィッテン,デイヴィッド | Conjugated polyelectrolyte and method of using the same |
US9750250B2 (en) | 2015-01-14 | 2017-09-05 | Stc.Unm | Conjugated polyelectrolytes and methods of using the same |
US10638759B2 (en) | 2015-01-14 | 2020-05-05 | University Of Florida Research Foundation, Inc. | Conjugated polyelectrolytes and methods of using the same |
WO2016115362A1 (en) * | 2015-01-14 | 2016-07-21 | Whitten David G | Conjugated polyelectrolytes and methods of using the same |
US10772851B2 (en) * | 2017-02-03 | 2020-09-15 | Aaron Kurt Neumann | Treatment and prevention of fungal infections |
US11154059B2 (en) | 2017-09-22 | 2021-10-26 | David G. Whitten | Substituted thiophene oligomers and polymers |
US11882831B2 (en) | 2017-09-22 | 2024-01-30 | Unm Rainforest Innovations | Substituted thiophene oligomers and polymers |
Also Published As
Publication number | Publication date |
---|---|
US20110293470A1 (en) | 2011-12-01 |
US9005540B2 (en) | 2015-04-14 |
WO2010054304A2 (en) | 2010-05-14 |
US20140086795A1 (en) | 2014-03-27 |
WO2010054304A3 (en) | 2010-07-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9005540B2 (en) | Conjugated polyelectrolyte capsules: light activated antimicrobials | |
Li et al. | Metal–organic-framework-based materials for antimicrobial applications | |
Shen et al. | Antibacterial applications of metal–organic frameworks and their composites | |
Bai et al. | N-halamine-containing electrospun fibers kill bacteria via a contact/release co-determined antibacterial pathway | |
Zhang et al. | Interfacial engineering of bimetallic Ag/Pt nanoparticles on reduced graphene oxide matrix for enhanced antimicrobial activity | |
Cai et al. | Insight into biological effects of zinc oxide nanoflowers on bacteria: why morphology matters | |
Zhang et al. | Potent antibacterial activities of Ag/TiO2 nanocomposite powders synthesized by a one-pot sol− gel method | |
US8834917B2 (en) | Nanoparticle composition and process thereof | |
Guan et al. | Novel photodegradable insecticide W/TiO2/Avermectin nanocomposites obtained by polyelectrolytes assembly | |
Gour et al. | Anti‐I nfectious Surfaces Achieved by Polymer Modification | |
JP5599470B2 (en) | Antifungal material | |
SK288876B6 (en) | Process for producing nanocomposite material with antibacterial properties, such material and its use | |
KR20110112274A (en) | A multi-effect antimicrobial surface coating forming material and its preparation | |
Ghosh et al. | Study of Antibacterial Efficacy of Hybrid Chitosan‐Silver Nanoparticles for Prevention of Specific Biofilm and Water Purification | |
Li et al. | Synthesis and characterization of biocompatible antimicrobial N-halamine-functionalized titanium dioxide core-shell nanoparticles | |
Gupta et al. | Cuprous oxide nanoparticles decorated fabric materials with anti-biofilm properties | |
Fiedot et al. | Deposition of one-dimensional zinc oxide structures on polypropylene fabrics and their antibacterial properties | |
DE112018000451B4 (en) | Process for producing a crosslinked polyethyleneimine coating and use of a crosslinked polyethyleneimine coating | |
US10584191B2 (en) | Antimicrobial star polymers with light-activated enhanced antimicrobial activity | |
Alharbi et al. | Antibiofilm activity of synthesized electrospun core-shell nanofiber composites of PLA and PVA with silver nanoparticles | |
Schutte-Smith et al. | Using visible light to activate antiviral and antimicrobial properties of TiO2 nanoparticles in paints and coatings: Focus on new developments for frequent-touch surfaces in hospitals | |
Olgun et al. | Preparation and antibacterial properties of nano biocomposite poly (ε-caprolactone)-SiO 2 films with nanosilver | |
Cui et al. | Near-infrared photodynamic antibacterial enhanced superhydrophobic electrospun membrane surfaces | |
Singh et al. | Scalable Hybrid Antibacterial Surfaces: TiO2 Nanoparticles with Black Silicon | |
Kalwar et al. | Incorporation of ciprofloxacin/laponite in polycaprolactone electrospun nanofibers: drug release and antibacterial studies |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UNIVERSITY OF FLORIDA RESEARCH FOUNDATION, INC., F Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SCHANZE, KIRK S.;OGAWA, MOTOKATSU;SOMMER, JONATHAN R.;SIGNING DATES FROM 20091208 TO 20100311;REEL/FRAME:024095/0076 |
|
AS | Assignment |
Owner name: THE REGENTS OF THE UNIVERSITY OF NEW MEXICO C/O RE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WHITTEN, DAVID;CORBITT, THOMAS;SIGNING DATES FROM 20110407 TO 20110411;REEL/FRAME:026726/0648 Owner name: STC.UNM, NEW MEXICO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE REGENTS OF THE UNIVERSITY OF NEW MEXICO C/O RESEARCH & TECHNOLOGY LAW;REEL/FRAME:026726/0662 Effective date: 20110519 |
|
AS | Assignment |
Owner name: THE REGENTS OF THE UNIVERSITY OF NEW MEXICO C/O RE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WHITTEN, DAVID G;CORBITT, THOMAS;SIGNING DATES FROM 20111025 TO 20111208;REEL/FRAME:027565/0263 Owner name: STC.UNM, NEW MEXICO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE REGENTS OF THE UNIVERSITY OF NEW MEXICO C/O RESEARCH & TECHNOLOGY LAW;REEL/FRAME:027565/0295 Effective date: 20120113 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
CC | Certificate of correction | ||
CC | Certificate of correction | ||
FEPP | Fee payment procedure |
Free format text: PAT HLDR NO LONGER CLAIMS MICRO ENTITY STATE, ENTITY STATUS SET TO SMALL (ORIGINAL EVENT CODE: MTOS); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2552); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 8 |